Physical properties of {Ti,Zr,Hf}2Ni2Sn compounds.

Physical properties, i.e. electrical resistivity (4.2-800 K), Seebeck coefficient (300-800 K), specific heat (2-110 K), Vickers hardness and elastic moduli (RT), have been defined for single-phase compounds with slightly nonstoichiometric compositions: Ti2.13Ni2Sn0.87, Zr2.025Ni2Sn0.975, and Hf2.055Ni2Sn0.945. From X-ray single crystal and TEM analyses, Ti2+xNi2Sn1-x, x ∼ 0.13(1), is isotypic with the U2Pt2Sn-type (space group P42/mnm, ternary ordered version of the Zr3Al2-type), also adopted by the homologous compounds with Zr and Hf. For all three polycrystalline compounds (relative densities >95%) the electrical resistivity of the samples is metallic-like with dominant scattering from static defects mainly conditioned by off-stoichiometry. Analyses of the specific heat curves Cpvs. T and Cp/T vs. T2 reveal Sommerfeld coefficients of γTi2Ni2Sn = 14.3(3) mJ mol-1 K-2, γZr2Ni2Sn = 10(1) mJ mol-1 K-2, γHf2Ni2Sn = 9.1(5) mJ mol-1 K-2 and low-temperature Debye-temperatures: θLTD = 373(7)K, 357(14)K and 318(10)K. Einstein temperatures were in the range of 130-155 K. Rather low Seebeck coefficients (<15 µV K-1), power factors (pf < 0.07 mW mK-2) and an estimated thermal conductivity of λ < 148 mW cm-1 K-1 yield thermoelectric figures of merit ZT < 0.007 at ∼800 K. Whereas for polycrystalline Zr2Ni2Sn elastic properties were determined by resonant ultrasound spectroscopy (RUS): E = 171 GPa, ν = 0.31, G = 65.5 GPa, and B = 147 GPa, the accelerated mechanical property mapping (XPM) mode was used to map the hardness and elastic moduli of T2Ni2Sn. Above 180 K, Zr2Ni2Sn reveals a quasi-linear expansion with CTE = 15.4 × 10-6 K-1. The calculated density of states is similar for all three compounds and confirms a metallic type of conductivity. The isosurface of elf shows a spherical shape for Ti/Zr/Hf atoms and indicates their ionic character, while the [Ni2Sn]n- sublattice reflects localizations around the Ni and Sn atoms with a large somewhat diffuse charge density between the closest Ni atoms.

Multicomponent diffusion in ionic crystals: theoretical model and application to combined tracer- and interdiffusion in alkali feldspar.

We present a model for multicomponent diffusion in ionic crystals. The model accounts for vacancy-mediated diffusion on a sub-lattice and for diffusion due to binary exchange of different ionic species without involvement of vacancies on the same sub-lattice. The diffusive flux of a specific ionic species depends on the self-diffusion coefficients, on the diffusion coefficients related to the binary exchanges, and on the site fractions of all ionic species. The model delivers explicit expressions for these dependencies, which lead to a set of coupled non-linear diffusion equations. We applied the model to diffusion of 23 Na, 39 K, and 41 K in alkali feldspar. To this end, gem-quality crystals of alkali feldspar were used together with 41 K doped KCl salt as diffusion couples, which were annealed at temperatures between 800 ∘ and 950 ∘ C. Concentration-distance data for 23 Na, 39 K, and 41 K were obtained by Time of Flight Secondary Ion Mass Spectrometry. Over the entire investigated temperature range the Na self-diffusion coefficient is by a factor of ≥ 500 higher than the K self-diffusion coefficient. Diffusion mediated by binary 39 K- 41 K exchange is required for obtaining satisfactory fits of the model curves to the experimental data, and the respective kinetic coefficient is well constrained.

Diffusion-controlled crack propagation in alkali feldspar.

The chemically driven propagation of interacting parallel cracks in monoclinic alkali feldspar was studied experimentally. Single crystals of potassium-rich gem-quality sanidine were shifted towards more sodium-rich compositions by cation exchange with a NaCl-KCl salt melt at a temperature of 850 ∘ C and close to ambient pressure. Initially, a zone with elevated sodium content formed at the crystal surfaces due to the simultaneous in-diffusion of sodium and out-diffusion of potassium, where the rate of cation exchange was controlled by sodium-potassium interdiffusion within the feldspar. A chemical shift of potassium-rich alkali feldspar towards more sodium-rich compositions produces highly anisotropic contraction of the crystal lattice. This induced a tensile stress state in the sodium-rich surface layer of the crystals, which triggered the formation of a system of nearly equi-spaced parallel cracks oriented approximately perpendicular to the direction of maximum shortening. Crack propagation following their nucleation was driven by cation exchange occurring along the crack flanks and was controlled by the intimate coupling of the diffusion-mediated build-up of a tensile stress state around the crack tips and stress release by successive crack propagation. The critical energy release rate of fracturing was determined as 1.8-2.2 J m - 2 from evaluation of the near-tip J-integral. The mechanism of diffusion-controlled crack propagation is discussed in the context of high-temperature feldspar alteration.

Boron-phil and boron-phob structure units in novel borides Ni3Zn2B and Ni2ZnB: experiment and first principles calculations.

The crystal structures of two novel borides in the Ni-Zn-B system, τ5-Ni3Zn2B and τ6-Ni2ZnB, were determined by single crystal X-ray diffraction (XRSC) in combination with selected area electron diffraction in a transmission electron microscope (SAED-TEM) and electron probe microanalysis (EPMA). Both compounds crystallize in unique structure types (space group C2/m, a = 1.68942(8) nm, b = 0.26332(1) nm, c = 0.61904(3) nm, ß = 111.164(2)°, RF = 0.0219 for Ni3Zn2B, and space group C2/m, a = 0.95296(7) nm, b = 0.28371(2) nm, c = 0.59989(1) nm, ß = 93.009(4)°, RF = 0.0163 for Ni2ZnB). Both compounds have similar building blocks: two triangular prisms centered by boron atoms are arranged along the c-axis separated by Zn layers, which form empty octahedra connecting the boron centered polyhedra. Consistent with the (Ni+Zn)/B ratio, isolated boron atoms are found in τ5-Ni3Zn2B, while B-B pairs exist in τ6-Ni2ZnB. The crystal structure of Ni2ZnB is closely related to that of τ4-Ni3ZnB2, i.e. Ni2ZnB can be formed by removing the nearly planar nickel layer in Ni3ZnB2 and shifting the origin of the unit cell to the center of the B-B pair. The electrical resistivity and specific heat of τ5-Ni3Zn2B reveal the metallic behavior of this compound with an anomaly at low temperature, possibly arising from a Kondo-type interaction. Further analysis on the lattice contribution of the specific heat reveals similarity with τ4-Ni3ZnB2 with some indications of lattice softening in τ5-Ni3Zn2B, which could be related to the increasing metal content and the absence of B-B bonding in τ5-Ni3Zn2B. For the newly found phases, τ5-Ni3Zn2B and τ6-Ni2ZnB as well as for τ3-Ni21Zn2B20 and τ4-Ni3ZnB2 density functional theory (DFT) calculations were performed by means of the Vienna Ab initio Simulation Package (VASP). Total energies and forces were minimized in order to determine the fully relaxed structural parameters, which agree very well with experiment. Energies of formations in the range of -25.2 to -26.9 kJ mol-1 were calculated and bulk moduli in the range of 179.7 to 248.9 GPa were derived showing hardening by increasing the B concentration. Charge transfer is discussed in terms of Bader charges resulting in electronic transfer from Zn to the system and electronic charge gain by B. Ni charge contributions vary significantly with crystallographic position depending on B located in the neighbourhood. The electronic structure is presented in terms of densities of states, band structures and contour plots revealing Ni-B and Ni-Zn bonding features.

The Ti-Mn system revisited: experimental investigation and thermodynamic modelling.

As the Ti-Mn phase diagram is part of numerous ternary and higher order systems of technological importance, the present paper defines phase relations which have been experimentally established throughout this work from 800 °C to the melting range based on Differential Thermal Analyses (DTA), X-ray powder diffraction, metallography and Electron Probe Micro Analysis (EPMA) techniques on ∼50 alloys, which were prepared by arc melting or high frequency melting under high purity argon starting from freshly cleaned metal ingots. Novel compounds were identified and reaction isotherms were redefined accordingly. In the Ti-rich region a novel compound TiMn was detected, sandwiched between the known phases: TiMn1-x (∼45 at% Mn) and TiMn1+x (∼55 at% Mn). In the Mn-rich region the hitherto unknown crystal structure of TiMn∼3 was solved from X-ray single crystal diffraction data and found to be of a unique structure type Ti6(Ti1-xMnx)6Mn25 (x = 0.462; space group Pbam (#55); a = 0.79081(3) nm, b = 2.58557(9) nm, c = 0.47931(2) nm), which consists of two consecutive layers of the hexagonal MgZn2-type Laves phase (TiMn2) and a combined layer of alternate structure blocks of MgZn2 type and Zr4Al3 type. Whereas TiMn can be considered as a line compound (solubility range <∼1 at%), the homogeneity regions of the Ti-Mn compounds are significant (determined by EPMA): TiMn1-x (44.0 to 46.6 at% Mn), TiMn1+x (54.6 to 56.3 at% Mn), Ti1+xMn2-x (MgZn2-type, 59 to 69 at% Mn at 1000 °C: -0.08 < x < 0.23), TiMn∼3 (unique type; 74 to 76.5 at% Mn) and TiMn∼4 (R-phase: Ti8(TixMn1-x)6Mn39, 80 to 84 at% Ti). Supported by ab initio calculations of the ground state energy for the Laves phase, the new experimental results enabled thermodynamic modelling of the entire Ti-Mn phase diagram providing a complete and novel set of thermodynamic data thus providing a sound basis for future thermodynamic predictions of higher order Ti-Mn-X-Y systems.

Ba-filled Ni-Sb-Sn based skutterudites with anomalously high lattice thermal conductivity.

Novel filled skutterudites BayNi4Sb12-xSnx (ymax = 0.93) have been prepared by arc melting followed by annealing at 250, 350 and 450 °C up to 30 days in vacuum-sealed quartz vials. Extension of the homogeneity region, solidus temperatures and structural investigations were performed for the skutterudite phase in the ternary Ni-Sn-Sb and in the quaternary Ba-Ni-Sb-Sn systems. Phase equilibria in the Ni-Sn-Sb system at 450 °C were established by means of Electron Probe Microanalysis (EPMA) and X-ray Powder Diffraction (XPD). With rather small cages Ni4(Sb,Sn)12, the Ba-Ni-Sn-Sb skutterudite system is perfectly suited to study the influence of filler atoms on the phonon thermal conductivity. Single-phase samples with the composition Ni4Sb8.2Sn3.8, Ba0.42Ni4Sb8.2Sn3.8 and Ba0.92Ni4Sb6.7Sn5.3 were used to measure their physical properties, i.e. temperature dependent electrical resistivity, Seebeck coefficient and thermal conductivity. The resistivity data demonstrate a crossover from metallic to semiconducting behaviour. The corresponding gap width was extracted from the maxima in the Seebeck coefficient data as a function of temperature. Single crystal X-ray structure analyses at 100, 200 and 300 K revealed the thermal expansion coefficients as well as Einstein and Debye temperatures for Ba0.73Ni4Sb8.1Sn3.9 and Ba0.95Ni4Sb6.1Sn5.9. These data were in accordance with the Debye temperatures obtained from the specific heat (4.4 K < T < 140 K) and Mössbauer spectroscopy (10 K < T < 290 K). Rather small atom displacement parameters for the Ba filler atoms indicate a severe reduction in the "rattling behaviour" consistent with the high levels of lattice thermal conductivity. The elastic moduli, collected from Resonant Ultrasonic Spectroscopy ranged from 100 GPa for Ni4Sb8.2Sn3.8 to 116 GPa for Ba0.92Ni4Sb6.7Sn5.3. The thermal expansion coefficients were 11.8 × 10(-6) K(-1) for Ni4Sb8.2Sn3.8 and 13.8 × 10(-6) K(-1) for Ba0.92Ni4Sb6.7Sn5.3. The room temperature Vickers hardness values vary within the range from 2.6 GPa to 4.7 GPa. Severe plastic deformation via high-pressure torsion was used to introduce nanostructuring; however, the physical properties before and after HPT showed no significant effect on the materials thermoelectric behaviour.

Ba5{V,Nb}12Sb19+x, novel variants of the Ba5Ti12Sb19+x-type: crystal structure and physical properties.

The novel compounds Ba5{V,Nb}12Sb19+x, initially found in diffusion zone experiments between Ba-filled skutterudite Ba0.3Co4Sb12 and group V transition metals (V,Nb,Ta), were synthesized via solid state reaction and were characterized by means of X-ray (single crystal and powder) diffraction, electron probe microanalysis (EPMA), and physical (transport and mechanical) properties measurements. Ba5V12Sb19.41 (a = 1.21230(1) nm, space group P4[combining overline]3m; RF(2) = 0.0189) and Ba5Nb12Sb19.14 (a = 1.24979(2) nm, space group P4[combining overline]3m; RF(2) = 0.0219) are the first representatives of the Ba5Ti12Sb19+x-type, however, in contrast to the aristotype, the structure of Ba5V12Sb19.41 shows additional atom disorder. Temperature dependent ADPs and specific heat of Ba5V12Sb19.41 confirmed the rattling behaviour of Ba1,2 and Sb7 atoms within the framework built by V and Sb atoms. Electrical resistivity of both compounds show an upturn at low temperature, and a change from p- to n-type conductivity above 300 K in Ba4.9Nb12Sb19.4. As expected from the complex crystal structure and the presence of defects and disorder, the thermal conductivity is suppressed and lattice thermal conductivity of ∼0.43 W m(-1) K(-1) is near values typical for amorphous systems. Vicker's hardness of (3.8 ± 0.1) GPa (vanadium compound) and (3.5 ± 0.2) GPa (niobium compound) are comparable to Sb-based filled skutterudites. However, the Young's moduli measured by nanoindentation for these compounds EI(Ba4.9V12Sb19.0) = (85 ± 2) GPa and EI(Ba4.9Nb12Sb19.4) = (79 ± 5) GPa are significantly smaller than those of skutterudites, which range from about 130 to 145 GPa.

Thermal, magnetic and electronic properties of non-centrosymmetric YbPt2B.

Ternary YbPt2B crystallizes in the non-centrosymmetric hexagonal CePt2B-type structure (space group P6(2)22). Electrical resistivity, specific heat and magnetic measurements reveal a magnetic instability at 5.6 K. Furthermore, a spin-reorientation of presumably a ferromagnetic type occurs around 1.5 K. The behaviour at low temperature is governed by a rather weak Kondo effect, T(K) ⩽ 1 K, in the presence of strong crystalline electric field splitting, with a doublet ground state. Besides, the complex magnetic behaviour presumably results from a Dzyaloshinskii-Moriya interaction triggered by the absence of inversion symmetry in the crystal structure. Scaling according to the de Gennes factor traces back magnetic ordering in YbPt2B to the Rudermann-Kittel-Kasuya-Yoshida (RKKY) interaction and the smooth evolution of the lattice constants and the unit cell volume of REPt2B (RE = rare earths) refers to the 4f(13) electronic configuration of Yb in YbPt2B.

Novel refractory phase, Ta7Si2(Si(x)B(1-x))2.

X-ray single crystal (XSC) and powder diffraction data (XPD) were used to elucidate the crystal structure of a new refractory silicon boride Ta7Si2(Si(x)B(1-x))2 (x = 0.12). Tetragonal Ta7Si2(Si(x)B(1-x))2 (space group P4/mbm; a = 0.62219(2) nm, c = 0.83283(3) nm) with B atoms randomly sharing the 4g site with Si atoms is isotypic with the boride structure of (Re,Co)7B4. The architecture of the structure of Ta7Si2(Si(x)B(1-x))2 combines layers of three-capped triangular metal prisms (Si,B)[Ta(6+2)(Si,B)] alternating with double layers of two-capped Si[Ta(8+1)Si] Archimedian metal antiprisms. Consequently, the metal framework contains (B/Si) pairs and Si-Si dumbbells. These two types of coordination figures around the nonmetal atoms are typical for the system-inherent structures of Ta2B (or Ta2Si) and Ta3B2. DFT calculations showed strong B(Si)-B(Si) and Si-Si bonding and represent Ta7Si2(Si(x)B(1-x))2 as a covalent-ionic compound. This bonding behavior is reflected in the high hardness value of 1750 HV. The Sommerfeld constant, γ = 7.58 mJ/mol K(2), as derived from the electronic density of states, calculated at the Fermi level, suggests typical metallic behavior.

Ti8(Ti(x)Mn(1-x))6Mn39 ('TiMn(~4)'): a metallic spin fluctuation system.

The crystal structure of Ti(8)(Ti(x)Mn(1-x))(6)Mn(39), x = 0.187, was obtained from x-ray single-crystal diffraction data, confirming it to have rhombohedral symmetry (space group [Formula: see text]; a(hex) = 1.100 70(2) nm, c(hex) = 1.944 11(4) nm; R(F) = 0.0293) and isotypism with the prototype Mo(0.38)Cr(0.16)Co(0.46) (the so-called R-phase). On the basis of electron probe micro-analyser results and structure determination, the homogeneity region of the phase TiMn(~4) was determined for temperatures in the range 800 °C < T < 1200 °C and is in between 16.0 at.% Ti and 20 at.% Ti. Various physical properties, determined in the temperature range from ~2 K to room temperature, characterize the compound with composition TiMn(4.26) as a metallic spin fluctuation system, evidenced from a T(3)lnT dependence of the heat capacity in combination with large values of the electronic Sommerfeld constant of the order of 140 mJ mol(-1) K(-2). The occurrence of a small anomaly in the heat capacity and magnetization data around 10 K is attributed to a scenario involving spin freezing phenomena, since a fraction of the order of 10% of all Mn-Mn distances within the unit cell are above a critical distance, where Mn atoms carry a spontaneous magnetic moment.

Type-I clathrate Ba8Ni(x)Si(46-x): phase relations, crystal chemistry and thermoelectric properties.

The phase relations, crystal structure and thermoelectric properties of the type-I solid solution Ba(8)Ni(x)Si(46-x) were investigated. Based on X-ray diffraction, differential thermal analysis and electron probe microanalysis data, a partial phase diagram was constructed for the Si-rich part of ternary system Ba-Ni-Si at 800 °C. The solubility range of Ni in the clathrate-I phase at 800 °C was determined (2.9 ≤x≤ 3.8) and thermoelectric properties, namely electrical resistivity, Seebeck-coefficient and thermal conductivity, were measured in the temperature range from 300 to 850 K. A shift of the thermoelectric properties from a predominantly metallic to a more semiconducting behavior was observed for an increasing Ni-content. Density functional calculations revealed a significant decrease of the gap width in the density of states induced by the incorporation of Ni. Electrical resistivity and Seebeck coefficients for Ba(8)Ni(x)Si(46-x) with 3.3 ≤x≤ 3.8 have been modeled within the rigid band approximation.

Crystal structure of novel compounds in the systems Zr-Cu-Al, Mo-Pd-Al and partial phase equilibria in the Mo-Pd-Al system.

The crystal structures of three Al-rich compounds have been solved from X-ray single crystal diffractometry: τ(1)-MoPd(2-x)Al(8+x) (x = 0.067); τ(7)-Zr(Cu(1-x)Al(x))(12) (x = 0.514) and τ(9)-ZrCu(1-x)Al(4) (x = 0.144). τ(1)-MoPd(2-x)Al(8+x) adopts a unique structure type (space group Pbcm; lattice parameters a = 0.78153(2), b = 1.02643(3) and c = 0.86098(2) nm), which can be conceived as a superstructure of the Mo(Cu(x)Al(1-x))(6)Al(4) type. Whereas Mo-atoms occupy the 4d site, Pd(2) occupies the 4c site, Al and Pd(1) atoms randomly share the 4d position and the rest of the positions are fully occupied by Al. A Bärnighausen tree documents the crystallographic group-subgroup relation between the structure types of Mo(Cu(x)Al(1-x))(6)Al(4) and τ(1). τ(7)-Zr(Cu(1-x)Al(x))(12) (x = 0.514) has been confirmed to crystallize with the ThMn(12) type (space group I4/mmm; lattice parameters a = 0.85243(2) and c = 0.50862(3) nm). In total, 4 crystallographic sites were defined, out of which, Zr occupies site 2a, the 8f site is fully occupied by Cu, the 8i site is entirely occupied by Al, but the 8j site turned out to comprise a random mixture of Cu and Al atoms. The compound τ(9)-ZrCu(1-x)Al(4) (x = 0.144) crystallizes in a unique structure type (space group P4/nmm; lattice parameters a = 0.40275(3) and c = 1.17688(4) nm) which exhibits full atom order but a vacancy (14.4%) on the 2c site, shared with Cu atoms. τ(9)-ZrCu(1-x)Al(4) is a superstructure of Cu with an arrangement of three unit cells of Cu in the direction of the c-axis. A Bärnighausen tree documents this relationship. The ZrCu(1-x)Al(4) type (n = 3) is part of a series of structures which follow this building principle: Cu (n = 1), TiAl(3) (n = 2), τ(5)-TiNi(2-x)Al(5) (n = 4), HfGa(2) (n = 6) and Cu(3)Pd (n = 7). A partial isothermal section for the Al-rich part of the Mo-Pd-Al system at 860 °C has been established with two ternary compounds τ(1)-MoPd(2-x)Al(8+x) and τ(2) (unknown structure). The Vickers hardness (H(v)) for τ(1) was found to be 842 ± 40 MPa.

Phase relations and crystal structure of τ6-Ti2(Ti(0.16)Ni(0.43)Al(0.41))3.

Ti(2)(Ti(0.16)Ni(0.43)Al(0.41))(3) is a novel compound (labeled as τ(6)) in the Ti-rich region of the Ti-Ni-Al system in a limited temperature range 870 < T < 980 °C. The structure of τ(6)-Ti(2)(Ti,Ni,Al)(3) was solved from a combined analysis of X-ray single crystal and neutron powder diffracton data (space group C2/m, a = 1.85383(7) nm, b = 0.49970(2) nm, c = 0.81511(3) nm, and ß = 99.597(3)°). τ(6)-Ti(2)(Ti,Ni,Al)(3) as a variant of the V(2)(Co(0.57)Si(0.43))(3)-type is a combination of slabs of the MgZn(2)-Laves type and slabs of the Zr(4)Al(3)-type forming a tetrahedrally close-packed Frank-Kasper structure with pentagon-triangle main layers. Titanium atoms occupy the vanadium sites, but Ti/Ni/Al atoms randomly share the (Co/Si) sites of V(2)(Co(0.57)Si(0.43))(3). Although τ(6) shows a random replacement on 6 of the 11 atom sites, it has no significant homogeneity range (~1 at. %). The composition of τ(6) changes slightly with temperature. DSC/DTA runs (1 K/min) were not sufficient to define proper reaction temperatures due to slow reaction kinetics. Therefore, phase equilibria related to τ(6) were derived from X-ray powder diffraction in combination with EPMA on alloys, which were annealed at carefully set temperatures and quenched. τ(6) forms from a peritectoid reaction η-(Ti,Al)(2)Ni + τ(3) + α(2) ↔ τ(6) at 980 °C and decomposes in a eutectoid reaction τ(6) ↔ η + τ(4) + α(2) at 870 °C. Both reactions involve the η-(Ti,Al)(2)Ni phase, for which the atom distribution was derived from X-ray single crystal intensity data, revealing Ti/Al randomly sharing the 48f- and 16c-positions in space group Fd3̅m (Ti(2)Ni-type, a = 1.12543(3) nm). There was no residual electron density at the octahedral centers of the crystal structure ruling out impurity stabilization. Phase equilibria involving the τ(6) phase have been established for various temperatures (T = 865, 900, 925, 950, 975 °C, and subsolidus). The reaction isotherms concerning the τ(6) phase have been established and are summarized in a Schultz-Scheil diagram.

The system uranium-palladium-boron with U(2.5)Pd(20.5)B(6), a new heavy fermion compound.

Phase equilibria in the system U-Pd-B were established at 850 °C by light optical microscopy (LOM) and x-ray powder and single crystal diffraction. Whereas in as-cast alloys only one ternary compound, τ(1)-U(2 + x)Pd(21 - x)B(6), was found to form at x ∼ 0.5, a further compound τ(2) with hitherto unknown structure was observed in alloys annealed at 850 °C. Due to the formation of suitable single crystals, the crystal structures of two binary compounds, UB(12) and UPd(3) have been redetermined from high precision x-ray data. Similarly, the crystal structure of τ(1)-U(2.5)Pd(20.5)B(6) was investigated by single crystal x-ray diffraction (XRD) revealing isotypism with the Cr(23)C(6)-type, (space group [Formula: see text]; a = 1.1687(5) nm; R(F)(2) = Σ|F(0)(2) - F(c)(2)|/ΣF(0)(2) = 0.021). τ(1)-U(2 + x)Pd(21 - x)B(6) is a partially ordered compound where 0.37(1)U + 0.63Pd atoms randomly share the 4a site in (0, 0, 0). Whereas mutual solubility of U-borides and Pd-borides was found at 850 °C to be below 1.0 at.%, a large homogeneity region of fcc-Pd(U, B) extends into the ternary system. U(2.5)Pd(20.5)B(6) has metallic behavior; the ground state properties are determined from a balance of the Kondo effect and the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction, revealing long range antiferromagnetic ordering below 6 K. An extraordinarily large Sommerfeld value (γ > 500 mJ mol(-1) K(-2)) groups U(2.5)Pd(20.5)B(6) among heavy fermion materials.

The formation, structure and physical properties of M(2)Pd(14+x)B(5-y) compounds, with M = La, Ce, Pr, Nd, Sm, Eu, Gd, Lu and Th.

Novel ternary compounds, M(2)Pd(14+x)B(5-y) (M =  La, Ce, Pr, Nd, Sm, Eu, Gd, Lu, Th; x∼0.9, y∼0.1), have been synthesized by arc melting. The crystal structures of Nd(2)Pd(14+x)B(5-y) and Th(2)Pd(14+x)B(5-y) were determined from x-ray single-crystal data and both are closely related to the structure type of Sc(4)Ni(29)B(10). All compounds were characterized by Rietveld analyses and found to be isotypic with the Nd(2)Pd(14+x)B(5-y) type. Measurements of the temperature dependent susceptibility and specific heat as well as the temperature and field dependent resistivity were employed to derive basic information on bulk properties of these compounds. The electrical resistivity of M(2)Pd(14+x)B(5-y), in general, is characterized by small RRR (residual resistance ratio) values originating from defects inherent to the crystal structure. Whereas the compounds based on Ce, Nd, Sm and Gd exhibit magnetic order, those based on Pr and Eu seem to be non-magnetic, at least down to 400 mK. While the non-magnetic ground state of the Pr based compound is a consequence of crystalline electric field effects in the context of the non-Kramers ion Pr, the lack of magnetic order in the case of the Eu based compound results from an intermediate valence state of the Eu ion.

Clathrates Ba(8){Zn,Cd}(x)Si(46-x), x∼7: synthesis, crystal structure and thermoelectric properties.

Novel ternary type-I clathrate compounds Ba(8){Zn,Cd}(x)Si(46-x), x∼7 have been synthesized from the elements by melting and reacting in quartz ampoules. Structural investigations for both compounds, i.e. x-ray single-crystal data at 300, 200 and 100 K for Ba(8)Zn(7)Si(39) and Rietveld data for Ba(8)Cd(7)Si(39), confirm cubic primitive symmetry consistent with the space group type [Formula: see text] (a(Ba(8)Zn(7)Si(39)) = 1.043 72(1) nm; a(Ba(8)Cd(7)Si(39)) = 1.058 66(3) nm). Whereas for Ba(8)Zn(7)Si(39) site 16i is completely occupied by Si atoms, a random atom distribution with different Zn/Si ratio exists for the two sites, 6d (0.77Zn+0.23Si) and 24k (0.91Si+0.09Zn). No vacancies are encountered and all atom sites are fully occupied. This atom distribution is independent of temperature. Rietveld refinements for Ba(8)Cd(7)Si(39) show that the 6d site is fully occupied by Cd atoms, leaving only the 24k site for a random occupation (0.96Si+0.04Cd) consistent with the chemical formula Ba(8)Cd(7)Si(39). The temperature-dependent x-ray spectra for Ba(8)Zn(7)Si(39) define an Einstein mode, Θ(E,U33) = 80 K. Studies of transport properties show electrons as the majority charge carriers in the system. Although the Cd- and Zn-based samples are isoelectronic, a significantly different electronic transport points towards substantial differences in the electronic density of states in both cases.

Superconductivity in novel Ge-based skutterudites: {Sr,Ba}pt4Ge12.

Combining experiments and ab initio models we report on SrPt4Ge12 and BaPt4Ge12 as members of a novel class of superconducting skutterudites, where Sr or Ba atoms stabilize a framework entirely formed by Ge atoms. Below T(c)=5.35 and 5.10 K for BaPt4Ge12 and SrPt4Ge12, respectively, electron-phonon coupled superconductivity emerges, ascribed to intrinsic features of the Pt-Ge framework, where Ge-p states dominate the electronic structure at the Fermi energy.

Crystalline electric field effects in the filled skutterudite compound PrOs4P12.

The filled skutterudite compound PrOs4P12 was synthesized in single-crystal form using a molten metal flux growth technique. Low-temperature magnetization, specific heat, and electrical resistivity measurements showed no indication of a phase transition down to 0.1 K but had features indicative of crystalline electric field (CEF) effects. Analyses of these features in terms of a cubic CEF suggest a Γ1 singlet or a Γ3 doublet ground state separated by 30-50 K from a Γ5 triplet first excited state.

Influence of chirality of the preceding acyl moiety on the cis/trans ratio of the proline peptide bond.

We report that the cis/trans ratio of the proline peptide bond can be strongly influenced by the chirality of the acyl residue preceding proline. Acyl moieties derived from (2S)-2,6-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid (8) and (2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoic acid (5) in acyl-Pro molecules influence isomerization of the proline peptide bond constraining the omega dihedral angle to the trans orientation. Structures of benzyl (2S)-1-([(2S)-2,6-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl)-2-pyrrolidinecarboxylate (3) derived from 2D (1)H NMR conformational analysis and crystallographic data exhibit only the trans conformation of proline peptide bond. On the other hand the diastereomer 4, which contains an (R) acyl moiety, exhibits two sets of signals in (1)H NMR spectra. The signals were assigned to trans (72%) and cis (28%) conformers. Crystallographic analysis of 4 showed that only the cis conformation is present in the crystalline state. The (1)H NMR chemical shift pattern of three sets of signals observed in 2 was observed also in benzyl (2S)-1-[(2R/S)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoyl]-2-pyrrolidinecarboxylate. (R)-Carboxylic acid 5, after coupling with (S)-ProOBn, yielded benzyl (2S)-1-[(2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoyl]-2-pyrrolidinecarboxylate (6), which in DMSO-d(6) exhibited only the trans conformation of the proline peptide bond. These results suggest that in these particular cases acyl-Pro peptide bond isomerization is strongly influenced by the stereochemistry of the acyl residue preceding proline. (2S)-2,6-Dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid (8) and (2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoic acid (5) are promising chiral peptidomimetic building blocks that can be used as acyl moieties to force the proline peptide bond into the trans conformation in a variety of acyl-Pro molecules.

Two dimeric CuII benzoate derivatives solvated with acetonitrile.

The title compounds, tetrakis(micro-benzoato-O:O')bis(2,6-diaminopyridine)-1kappaN,2kappaN-dicopper(II)-acetonitrile (1/2), [Cu(2)(C(7)H(5)O(2))(4)(C(5)H(7)N(3))(2)].2C(2)H(3)N, (I), and bis(acetonitrile)-1kappaN,2kappaN-tetrakis(micro-benzoato-O:O')dicopper(II)-acetonitrile (1/1.5), [Cu(2)(C(7)H(5)O(2))(4)(C(2)H(3)N)(2)].1.5C(2)H(3)N, (II), crystallize as acetonitrile solvates exhibiting different stability. They have similar molecular structures with discrete dimeric units located at crystallographic inversion centres. The copper ions are bridged by four benzoate groups and neutral N-donor ligands, viz. 2,6-diaminopyridine in (I) and acetonitrile in (II), are coordinated at apical positions. The diverse stability is probably due to hydrogen-bond interactions of the solvated acetonitrile molecules with neighbouring dimers in compound (I).